Process for preparing spray dried detergent compositions

ABSTRACT

A PROCESS IS PROVIDED FOR PREPARING SPRAY DRIED SUBSTANTIALLY HOMOGENEOUS DETERGENT COMPOSITIONS FROM AQUEOUS SLURRIES CONTAINING SURFACE-ACTIVE ETHYLENE OXIDE ADDUCTS WHEREIN PRIOR TO SPRAY DRYING THE AQUEOUS SLURRY, AN ORGANIC MONO- OR POLYPHOSPHATE ESTER IS INCORPORATED WITH THE SURFACE-ACTIVE ETHYLLENE OXIDE ADDUCT AND OTHER INGREDIENTS EMPLOYED IN THE DETERGENT COMPOSITION, IN ORDER TO INHIBIT THE SLURRY FROM SEPARATING INTO DIFFERENT LAYERS SO THAT THE PARTICULATE DETERGENT COMPOSITION PRODUCTED WILL BE SUBSTANTIZLLY HOMOGENEOUS AND LOW FOAMING AND HAVE GOOD CLEANING POWER. THE PHOSPHATE ESTER MAY BE ADDED TO THE INGREDIENTS OF THE DETERGENT COMPOSITION PRIOR TO, DURING OR SUBSEQUENT TO THE PREPARATION OF THE AQUEOUS SLURRY TO THE INGREDIENTS. DETERGENT COMPOSITIONS ARE ALSO PROVIDED, WHICH CAN BE PREPARED EMPLOYING THE ABOVE PROCESS, CONSISTING ESSENTIALLY OF AT LEAST ONE SURFACE-ACTIVE ETHYLENE OXIDE ADDUCT, AND AN ORGANIC MONO- OR POLYPHOSPHATE ESTER, AND OPTIONALLY, INORGANIC BUILDERS, OPTICAL WHITENERS, CHELATING AGENTS AND DIRT CARRIERS, SUCH AS CARBOXYMETHYL CELLULOSE.

United States Patent Oflice 3,741,913 Patented June 26, 1973 3,741,913 PROCESS FOR PREPARING SPRAY DRIED DETERGENT COMPOSITIONS Ake Waag, Stenungsund, Sweden, assignor to M och Domsjo Aktiebolag, Ornskoldsvik, Sweden No Drawing. Continuation of abandoned application Ser. No. 648,248, June 23, 1967. This application Feb. 19, 1971, Ser. No. 117,073 Claims priority, application Sweden, June 23, 1966, 8,678/ 66 Int. Cl. Clld 3/36 U.S. Cl. 252-544 14 Claims ABSTRACT OF THE DISCLOSURE A process is provided for preparing spray dried substantially homogeneous detergent compositions from aqueous slurries containing surface-active ethylene oxide adducts wherein prior to spray drying the aqueous slurry, an organic monoor polyphosphate ester is incorporated with the surface-active ethylene oxide adduct and other ingredients employed in the detergent composition, in order to inhibit the slurry from separating into different layers so that the particulate detergent composition produced will be substantially homogeneous and low foaming and have good cleaning power. The phosphate ester may be added to the ingredients of the detergent composition prior to, during or subsequent to the preparation of the aqueous slurry of the ingredients.

Detergent compositions are also provided, which can be prepared employing the above process, consisting essentially of at least one surface-active ethylene oxide adduct, and an organic monoor polyphosphate ester, and optionally, inorganic builders, optical whiteners, chelating agents and dirt carriers, such as carboxymethyl cellulose.

This application is a continuation of copending application Ser. No. 648,248, filed June 23, 1967 and now abandoned.

The present invention is concerned with a method for preparing spray dried detergent compositions from aqueous slurries containing surface active ethylene oxide adducts and organic and inorganic builders.

Detergent compositions suitable for use in modern washing machines and for synthetic fabrics require surface active substances possessing particularly good qualities with regard to low foaming ability, strong cleaning ability and a small afiinity for the fabric. Surfactants which possess such properties are ethylene oxide adducts of different chemical substances, such as alkyl phenols, fatty alcohols, fatty acids, fatty acid alkanol amides and alkyl mercaptans and ethylene oxide-propylene oxide block polymers. In addition to the just mentioned ethylene oxide adducts large quantities of builders comprised of organic and/ or inorganic substances are included in such detergents. The inorganic substances are primarily comprised of water-soluble alkaline builder salts, such as phosphates for instance alkali metal tripolyphosphates, alkali metal silicates, alkali metal borates, alkali metal carbonates, alkali metal hydrocarbonates, alkali metal sulphates, alkali metal chlorides etc., and inorganic peroxides (bleaching agents), whereas the organic substances comprise optical whiteners, dirt carriers such as carboxymethyl cellulose, and chelating agents, such as ethylene diamine tetraacetic acid etc. When preparing the detergent composition the ingredients are first mixed with water and, because of the high substance concentration (40-60 percent by weight), a slurry is obtained, which is then dried in heat to powder form. The drying method adopted is the spray drying method; the slurry being ejected under high pressure through a nozzle in the top of a tower and allowed to flow downwards whilst coming into contact with hot air, whereby small granules of detergent composition are formed. It is important that these granules have the same composition throughout, so that a detergent possessing good and reproducible properties is obtained. However, when preparing detergent compositions containing ethylene oxide adducts difficult problems present themselves during the spray drying process, in that the slurry to be dried is not sufficiently stable and often separates into different layers; whereby the homogeneity of the dried composition is jeopardized and there is also a risk that the nozzles will become blocked. Before the slurry can be sprayed it is necessary that it remains stable for at least one minute upon completion of the agitating process. Attempts have been made to alleviate these problems, which are not so much concerned with the solubility in water of the ingredients forming a part of the slurry as with their ability of together forming stable slurries or aqueous dispersions by strong agitation or by the addition of different substances; but hitherto these methods have given rise to appreciable disadvantages in the form of incomplete and deficient dispersion, increased foam formation, decrease in the cleansing ability of the composition, and high cost.

The present invention is intended to eliminate or substantially reduce the above mentioned deficiencies encountered in the preparation of spray dried detergent compositions of aqueous slurries containing surface active ethylene oxide adducts and conventional builders. It has been found that the said disadvantages are, according to the invention, surprisingly eliminated if, prior to, during or subsequent to preparing the aqueous slurry, one or more known phosphate esters, possibly condensed as condensate with two, three or four groups of the general formula or alkali salts or ammonium salts thereof are added to the slurry, in which formula R and R are alike or different and represent hydrogen or a group where R represents a saturated or unsaturated, straight or branched alkyl or alkenyl radical having a total of 4-22, preferably 8-18, carbon atoms in the alkyl or alkenyl portion or a mono, di or trialkyl substituted phenol having a total of 6-24, preferably 8-18 carbon atoms in the alkyl portion, wherewith R and R do not at the same time comprise hydrogen, and n is -30, preferably 5-25; after which the obtained slurry is spray dried in a manner known per se. The addition of such phosphate esters has been found to impart a very good stability to the slurry, in addition there occurs no depreciation in the cleansing ability of the detergent composition, nor does it give rise to heavy foam formation. The compounds can be produced at a relatively low price and have Such a strong efifect that only small amounts need be added, and the requirement of additional additives in the form of other substances such as hydrotropes and solubilizers is unnecessary.

The phosphate esters which may be used according to the invention may be prepared by phosphating in a known manner compounds including a residue having the gen eral formula wherein R and ll have the above disclosed significance. Such compounds are suitably ethylene oxide adducts of mono, di or trialkyl substituted phenols with a total of 6-24, preferably 25-18, carbon atoms in the alkyl portion and preferably 6-30 moles ethylene oxide such as nonylphenol having 8-1-6 moles ethylene oxide, dinonylphenol having 8-16 moles ethylene oxide, tri-sec.-butylphenol having 10-30 moles ethylene oxide, octylphenol having 8-16 moles ethylene oxide, octylcresol having 8- moles ethylene oxide.

Other suitable compounds are ethoxylated, saturated or unsaturated primary aliphatic alcohols having preferably 8-18 carbon atoms and preferably 3-20 moles eth-.

ylene oxide, for instance coconut fatty alcohol having 6-10 moles ethylene oxide, oleyl alcohol having 10-20 moles ethylene oxide, tridecylalcohol having 10-20 moles ethylene oxide, cetylstearyl alcohol having 10-30 moles ethylene oxide etc.

Additional compounds which are suitable for producing the phosphate esters are such where n in the above formula is 0, Le. nonethoxylated compounds containing the residue R defined according to the above, such as mono, di or trialkyl substituted phenols, and saturated or unsaturated primary aliphatic alcohols. Examples of such compounds are nonyl phenol, dinonyl phenol, trisec.-butyl phenol, 2-ethyl hexanol, dodecylalcohol, cetyl alcohol, stearylalcohol, oleyl alcohol, tridecyl alcohol etc.

As starting material for the phosphating process, mixtures of the above mentioned compounds may also used, e.g. mixtures of ethoxylated compounds and also mixtures of ethoxylated and nonethoxylated products. With regard to such mixtures it is particularly suitable to phosphatize mixtures of ethoxylaed alkyl phenols having a total of 6-24, preferably 8-18 carbon atoms in the alkyl portion and primary, aliphatic, straight or branched alcohols having 4-8 carbon atoms; the mole ratio of ethoxylated alkylphenol/aliphatic alcohol being from 1:1 to 1:9.

An example of such a mixture is a mixture containing nonyl phenol having 6 moles ethylene oxide and 2-ethylhexanol, in the mole ratio of about 1:1. Another example is a mixture of oleyl alcohol having 14 moles ethylene oxide and tridecyl alcohol having 8 moles ethylene oxide in the mole ratio of 1:1.

An example of phosphating agents used in preparing the phosphate esters are polyphosphoric acid (partially hydrated P 0 retailed by Stauffer Chemical Co.), P 0 and H PO Mixtures of other phosphating agents may also be used. In the esterifying reaction, the phosphating agent is reacted at an elevated temperature, preferably 50-100 C., with the compound or compounds to be phosphated, preferably for a period of time of from 0.5- 4 hours, after which the formed acid product is preferably neutralized with alkali hydroxide or NH whereby the neutralizing process may be effected before, or dur ing the preparation of the slurry to be spray dried. The mole ratio of phosphating agent/phosphating mixture is 4 of great importance and varies according to the composition of the phosphating mixture and the phosphating agent used. It is generally suitable to cause 1-5 moles of phosphating agent to react with 1-5 moles of the organic compound. When using polyphosphoric acid (73-85 percent by weight P 0 as the phosphating agent or phosphating ethoxylated alkyl phenols and/or primary aliphatic alcohols it is particularly expedient that the amount of polyphosphoric acid comprises 1-l.5 moles per mole ethoxylated alkyl phenol. When using phosphoric acid as the phosphating agent it is particularly advantageous with regard to the phosphating of mixtures of ethoxylated alkyl phenols and primary aliphatic alcohols if the mole ratio of P O /phosphating mixture is from 1:3 to 1.5:3 and the mole ratio ethoxylated alkyl phenol/ primary aliphatic alcohol lies between 1:1 and 1:9. It is also of particular advantage in this connection if the mole ratio P O /ethoxylated alkylphenol is less than 1:2. A mixture of phosphating esters having the above disclosed formula is generally obtained during the phosphating reaction, whereby monoesters, diesters or triesters are obtained, according to the prevailing reaction conditions, the constituents taking part in the reaction and the amount of phosphating agent. When phosphating with a polyphosphoric acid of an alcohol or an ethylene oxide adduct a mixture of mono and diesters is usually obtained; monoesters forming the predominate percentage of the mixture. When conducting such a phosphating process smaller amounts of polyphosphoric esters are also obtained e.g. in the form of pyrophosphoric acid diesters, polyphosphoric acid triesters, triphosphoric acid diesters etc., which may, of course also be used according to the present invention. When phosphating a mixture of ethylene oxide adducts and aliphatic alcohols with orthophosphoric acid a mixture is obtained, which contains primarily diesters. It is impossible to obtain exact information concerning the compostion of the phosphating mixtures due to the fact that as yet, no suitable analysis method for this purpose has been suggested. During such phosphating reactions insignificant amounts of triesters are also formed; which naturally may also be included in the phosphate ester mixture added according to the invention.

Suitable surface active ethylene oxide adducts which can be used in the detergent compositions according to the present invention are ethylene oxide adducts of alkyl phenols, fatty acids, fatty alcohols, fatty acid alcohol amides, alkyl mercaptans and ethylene oxide/propylene oxide block polymers. An example of such adducts are mono, di and trialkylphenols having l-50 moles ethylene oxide and a total of 8-22 carbon atoms in the alkyl portion, primary, aliphatic alcohols having 1-100 moles ethylene oxide and a saturated or unsaturated, straight or branched alkyl or alkenyl portion having a total of 8-22 carbon atoms, alkyl mercaptans having 1-50 moles ethylene oxide, fatty acid mono or di-alkanol amides having 1-10 moles ethylene oxide and saturated or unsaturated, straight or branched alkyl or alkenyl portion with a total of 8-22 carbon atoms and the alkanol portion deriving from ethanol, propanol or butanol groups, ethylene oxide/propylene oxide block polymers, where the polypropylene oxide portion or portions comprise the hydrophobic portion and polyethylene oxide the hydrophilic portion. According to the present invention mixtures of the above mentioned products are also suitable. Naturally the effect of the phosphate ester additive according to the present invention is also present when the surface active ethylene oxide adduct is used together with other types of surfactants, e.g. together with soap, alkyl aryl sulphonates, alkyl sulphates, alkyl sulphonates, alkyl isothionates, alkyl taurides, alkyl phenol ether sulphonates, alkyl phenol ether sulphates, alkyl ether sulphates, alkyl naphthalene sulphonates, sulphonates of naphthalene formaldehyde condensates, carboxymethylated alkyl or alkyl phenol ethylene oxide adducts etc.

The above disclosed water-soluble alkaline builders included in the detergent composition generally comprise 30-60% of the weight of the slurry. Typical formulations of the ingredients in the slurry are given below:

Percent by weight Surface active agent 5-20 Dirt carrier, e.g. carboxymethyl cellulose 0.5-2.5

Bleaching agent, e.g. alkali metal perborate 5-20 Builder I, e.g. sodium silicate 38-40 B 5-20 Builder II, e.g. sodium sulphate 5-20 Builder III, e.g. sodium tripolyphosphate 10-50 Water 30-60 Suitable amounts of phosphate esters required for achieving the effect according to the invention are from 1 to 50% calculated on the amount of surface active agent included in the composition, preferably 5-25% by weight being used. The addition of the phosphate esters may be effected at any time during the slurrying process, i.e. during any of the steps taken in mixing the various ingredients; but it is also possible to add the phosphate esters to any of the ingredients, e.g. the surface active agent, before preparing the slurry, likewise as it is also possible to add the phosphate esters in question to the prepared slurry. The phosphate esters are preferably added during the preparation of the slurry, which gives the advantage that the included surface active ethylene oxide adduct does not salt out at any time during the procedure.

Although, as a rule, additions of very small amounts of phosphate esters give a satisfactory result (as can be seen from the following examples) it is, if desired, possible to add to the slurry other substances such as benzene sulphonate, alkyl benzene sulphonates, toluene sulphonate, xylene sulphonate, alkyl naphthalene sulphonates, carbamide, dicyanamide, amino oxides, propylene glycol, hexylene glycol, which increase the solubility of the ethylene oxide adduct in solvents, for instance water. It should also be mentioned, however, that the nature of the effect of such substances is different from the elfect of the phosphate esters added according to the present invention, which have a special and surprising effect in aqueous slurries containing surface active ethylene adducts and high concentrations of electrolytes.

The invention is illustrated in the following examples.

EXAMPLE 1 In a containing 100 parts by weight water the following ingredients were slurried unter agitation, in the given order:

Parts by weight (1) Dinonyl phenol, 16 moles ethylene oxide 15 (2) Sodium carboxymethyl cellulose 1 (3) Water glass 38-40 B. 15 (4) Sodium sulphate 29 (5) Sodium tripolyphosphate 40 The slurry was then heated to 80 C., the ethylene oxide adduct salted out after 10 seconds. When 10% by weight of the ethylene oxide adduct (1.5 parts by weight) was exchanged against the sodium salt of an esterification product of 1.3 moles polyphosph'oric acid (calculated as P and 1 mole nonylphenol having 8 moles ethylene oxide but otherwise under the same conditions no salting out could be observed during an observation period of 30 mins., and the slurry proved to be completely stable and intact. When sprayed dried it gave a homogeneous powder.

EXAMPLE 2 Example 1 was repeated but with an addition of 10% by weight calculated on the amount of ethylene oxide adduct (1.5 parts by weight) of the potassium salt of a phosphate ester obtained by reacting 1.3 moles polyphosphoric acid (calculated as P 0 with 1 mole nonylphenol having 12 moles ethylene oxide. No separation was observed during an observation period of 30 mins. upon the addition of the phosphate ester according to the invention. The slurry according to the invention gave a homogeneous powder upon subsequent spray drying.

EXAMPLE 3 Example 1 was repeated but with an addition of 10% by weight calculated on the amount of ethylene oxide adduct of potassium salt of a phosphate ester obtained by reacting 1.3 moles polyphosphoric acid (calculated as P 0 and 1 mole nonylphenol having 16 moles ethylene oxide. When adding the phosphate ester according to the invention no separation could be noticed during an observation period of 30 mins. The slurry gave a homogeneous powder when subjected to spray drying process.

EXAMPLE 4 A slurry was prepared containing 19 parts by weight of water and the following ingredients added in the order given below:

Parts by weight (1) Nonyl phenol with 10 moles ethylene oxide 10 (2) Sodium carboxymethyl cellulose 1.5 (3) Water glass 38 B. 30.5 (4) Sodium sulphate 35.0

When heating to C. a separation was observed after only 10 secs. When 30% by weight (3 parts by weight) of the ethylene oxide adduct was exchanged against a phosphate ester obtained by reacting 0.34 mole orthophosphoric acid and 1.5 moles P 0 on one side and a mixture of 1.1 moles nonyl phenol having 6 moles ethylene oxide and 1.9 moles Z-ethyl hexanol on the other side, which was neutralized with NaOH to pH 8.5 (in one percent aqueous solution), no separation was observed during an observation period of 30 mins. The slurry prepared according to the invention gave a homogeneous product when subjected to a spray drying operation.

EXAMPLE 5 A slurry was prepared containing 110 parts by weight of water and the following ingredients. The phosphate ester was added in a first stage, whereupon the ingredients were added in the order given below:

(5) Sodium tripolyphosphate Parts by weight (1) Phosphate ester according to Example 2 3.6 (2) Coconut fatty alcohol having 7 moles ethylene oxide 14.4 (3) Sodium carboxymethyl cellulose 1.0 (4) Water glass 38 B. 5.0 (5) Sodium sulphate 40.0 (6) Sodium tripolyphosphate 31.0 (7) Sodium perborate 5.0

The obtained slurry was stable during the complete preparation period and when heated to 80 C. no signs of separation were noticed after an observation period of 30 mins. The slurry gave a homogeneous powder when sub- -jected to a spray drying operation.

EXAMPLE 6 EXAMPLE 7 A slurry was prepared of parts by weight of water and the following ingredients added in the order in which they appear.

Parts by weight (1) Oleyl alcohol with 14 moles ethyl oxide 6 .5- (2) Tridecyl alcohol having 8 moles ethylene oxide 6.5 (3) Sodium carboxymethyl cellulose 1.0 (4) Water glass 40 B. 15.0 (5) Sodium carbonate 30.0 (6) Sodium tripolyphosphate 39.0

Subsequent to slurrying the said ingredients 2.0 parts by Weight of the sodium salt of a phosphate ester obtained by reacting 1.5 moles polyphosphoric acid (calculated as P and 2.3 moles 2-ethyl hexanol was added. When heated to 80 C. no signs of separation were observed during an observation period of 30 mins. and the said slurry gave a homogeneous powder when subjected to a spray drying operation.

Having regard to the foregoing disclosures, the following is claimed as the inventive and patentable embodiments thereof:

1. A process for preparing a substantially homogeneous spray dried detergent composition from an aqueous slurry containing about 30% to about 60% by weight of water and having solid ingredients consisting essentially of about 5% to about 20% by weight of a surface-active ethylene oxide adduct of an alkyl phenol, fatty alcohol, fatty acid alkanol amide, alkyl mercaptan or an ethylene oxidepropylene oxide block polymer, and about 30% to about 60% by weight of water-soluble inorganic alkaline builder salts, said slurry having a tendency to separate into phases, which process comprises incorporating in said slurry prior to spray drying an amount to inhibit phase separation within the range from about 1 to about 50% by weight based on the surface-active ethylene oxide adduct of an organic phosphate ester having the general formula:

wherein R and R can be the same or different and are selected from the group consisting of hydrogen and R(OCH CH wherein R is selected from the group consisting of alkyl and alkenyl radicals containing from about four to about twenty-two carbon atoms, and a mono-, dior trialkyl-substituted phenyl, the allyl containing from about six to about twenty-four carbon atoms, at least one of R and R being R(OCH CH and n is an integer from 0 to about 30; and spray-drying the aqueous slurry to form particles of uniform composition.

2. A process in accordance with claim 1 which comprises incorporating the organic phosphate ester in the detergent composition while adding water to the ingredients to form a slurry thereof.

3. A process in accordance with claim 1 which comprises adding the organic phosphate ester to the aqueous slurry of the detergent composition.

4. A process in accordance with claim 1 which comprises incorporating the organic phosphate ester with the detergent composition prior to adding water to the ingredients to form a slurry thereof.

5. A process in accordance with claim 1, wherein the organic phosphate ester is selected from the group consisting of alkali metal salts and ammonium salts of such phosphate esters.

6. A substantially homogeneous spray dried detergent composition consisting essentially of about 5 to about 20 parts by Weight of at least one surface-active ethylene oxide adduct of an alkyl phenol, fatty-alcohol, fatty acid, fatty acid alkanol amide, or alkyl mercaptan or an ethylene oxide-propylene oxide block polymer; about 30 to about 60 parts by weight of water soluble inorganic alkaline builder salts; and from about 1 to about 50% by weight based on the surface-active ethylene oxide adduct of an organic phosphate ester having the general formula:

Ri-O r O l) [RrO O-H] wherein R and R can be the same or different and are selected from the group consisting of hydrogen and R(OCH CH wherein R is selected from the group consisting of alkyl and alkenyl radicals containing from about four to about twenty-two carbon atoms, and a mono-, dior trialkyl-substituted phenyl, the alkyl containing from about six to about twenty-four carbon atoms, at least one of R and R being R(0C'H CH and n is an integer from 0 to about 30.-

7. A substantially homogeneous spray dried detergent composition in accordance with claim 6 wherein the organic phosphate ester is selected from the group consisting of alkali metal salts and ammonium salts of such organic phosphate esters.

8. A substantially homogeneous spray dried detergent composition in accordance with claim 6 wherein at least one of R and R is a mono-, dior trialkyl-substituted phenyl having from about eight to about eighteen carbon atoms in the alkyl portion.

9. A substantially homogeneous spray dried detergent compositon in accordance with claim 6 wherein at least one of R and R is alkyl having from about eight to about eighteen carbon atoms.

10. A substantially homogeneous spray dried detergent composition in accordance with claim 6 wherein at least one of R and R is derived from mixtures of ethoxylated alkyl phenols containing from about six to about twentyfour carbon atoms in the alkyl portion and primary, aliphatic, straight or branched alcohols containing from about four to about eight carbon atoms.

11. A substantially homogeneous spray dried detergent composition in accordance with claim 10 in which the ethoxylated alkyl phenol and the aliphatic alcohol are present in a mol ratio of about 1:1 to about 1:9.

12. A slurry adapted upon spray drying to yield homogeneous detergent particles, consisting essentially of about 5% to about 20% of a surface-active ethylene oxide adduct of an alkyl phenol, fatty alcohol, fatty acid alkanol amide, alkyl mercaptan or an ethylene oxide-propylene oxide block polymer; and from about 30% to about 60% by weight of water-soluble inorganic alkaline builder salts; slurried in from about 30% to about 60% by weight of water; said slurry having a tendency to separate into phases; and an amount sufficient to inhibit phase separation within the range of from about 1% to about 50% by weight based on the surface-active ethylene oxide adduct of an organic phosphate ester having the general wherein R and R can be the same or different and are selected from the group consisting of hydrogen and R(OCH CH wherein R is selected from the group consisting of alkyl and alkenyl radicals containing from aboutfour to about twenty-two carbon atoms, and a mono-, dior trialkyl-substituted phenyl, the alkyl containing from about six to about twenty-four carbon atoms, at least one of R and R being R(OCH CH and n is an integer from 0 to about 30.

13. A slurry in accordance with claim 12 and also containing from about 0.5% to about 2.5% by'weight of sodium carboxymethyl cellulose.

14. A slurry in accordance with claim 12 and also containing from about to about 20% by weight of a bleaching agent.

References Cited UNITED STATES PATENTS 5 11/1967 Behrens 252-137 12/1966 Dupre et a1. 252-135 1/1968 Cooper et al. 252-99 9/1964 Schlitz et a1. 252-137 9/ 19 68 Quimby 252-89 X 8/1964 Inamorato 252-138 6/1967 Inamorato 252-135 X 6/ 1965 Metcalf et a1. 252-135 2/1964 Grifo et a1. 252-135 10 OTHER REFERENCES General Aniline & Film Corp., Tech. Bulletin 7543- 094; GAFAC Surfactants, :610, PE 510, 1.0529, 1960.

Mayhew et al.: Phosphate Surfactants-Properties and Uses, Soap and Chemical Specialties, April 1962, pp. -58, 95, 93; May 1962, pp. -81, 167, 169.

HERBERT B. GUYNN, Primary Examiner H. A. PITLICK, Assistant Examiner US. Cl. X.R. 252-89, 525

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Dated lacent No. 3, 741,913 I l'uveucofle) A .Waag

' June 26, 1973 It is certified that error appears in theabove-identified patent: and that said Letters Patent ere hereby corrected as shown below:

' Column 3; line 4'7 ,Column 5, line 49 Column 3, line 51 Column 4, line 3'7 Column 5, line 48 1 Column 5, line 67 Column 7, line 48,

Claim 1 -"In a containing" should "be -;--In container containing-- 'also used" -;should be -al'so' be used-- "ethoxylaed should be --et hoxylated-- "compost ion" should be --composit ion-- "unter" sliould be --un'der- "sprayed" should be --sprayf:- f

"'allylf" should be -la1k '1-5Q Signed and sealed this 2nd day, of' ril 1m.

(SEAL) Attest:

EDWARD M .FLETCHER, JR Attesting Officer C MARSHALL DANN C'ommi s si oner of Pate nt s 

